Method for forming fine structure of a group of metal fine particles

ABSTRACT

A method for forming a fine structure of metal fine particles includes a step [FIG.  1 ( a )] of substituting a part of metal fine particles stabilized by a dispersion stabilizer desorbed when irradiated with an electromagnetic wave of high energy and/or high energy density and a dispersing agent from the surface of the metal fine particles when irradiated with an electromagnetic wave of a lower energy and/or a lower energy density and/or a compound having no bonding ability to the metal fine particles so as to prepare a colloidal solution of the metal fine particles, irradiating the colloidal solution with the electromagnetic wave of high energy and/or high energy density, and thereby improve the photosensitivity of the metal fine particles dispersed solution, and a step [FIG.  1 ( b )] of irradiating the metal fine particles dispersed solution having the improved photosensitivity with an electromagnetic wave of a lower energy and/or a lower energy density, and fixing the metal fine particles to a desired fine structure corresponding to the irradiation with the electromagnetic wave of the lower energy and/or the lower energy density on the surface of a substrate.

FIELD OF THE INVENTION

The present invention relates to a method to form activated andphotosensitized metal fine particles dispersion comprising, irradiatingelectromagnetic wave of high energy and/or electromagnetic wave of highenergy density to a dispersion of metal fine particles and fixing a finemetal from said metal fine particles which is flocculated by irradiationof electromagnetic wave of lower energy and/or electromagnetic wave oflower energy density than said electromagnetic wave on surface of asubstrate, and relates to a method to flocculate and fix said metalparticles by desired fine structure on surface of a substratecomprising, a process to flocculate metal fine particles by irradiatingsaid electromagnetic wave of low energy and/or electromagnetic wave oflow energy density to said activated and photosensitized metal fineparticles dispersion.

BACK GROUND OF THE ART

Fine particles of a noble metal, for example, fine particles of gold ispaid attention to as a base material to form various functionalmaterials. In particular, a substrate consisting of said metal fineparticles or a substrate which forms said metal fine particles on thesurface is utilized in broad fields, because said substrates have aneffect which said metal fine particles peculiarly own and a function tobond a compound which has an affinity group to said metal byself-organization, by non-covalent bond or by covalent bond.

In said circumstance, the inventors of the present invention alreadyproposed methods to fix above metal particles on various substratescomposed of transparent or not transparent material to the light havinglonger wavelength than UV ray.

For example, the inventors of the present invention have alreadydeveloped and proposed a technique to fix metal particles from adispersion of metal fine particles by dipping a substrate into organicsolvent dispersion of metal fine particles and by irradiating a laserbeam of wavelength from ultra violet to near-infra red region (JapanesePatent Laid-Open Publications 2001-149774, 2002-88487).

However, in these methods, since so called the light belonging to theregion from UV to near-infra red is used, fixing of metal particles isrestricted to the surface area where said light reaches, and it isimpossible to fix metal fine particles to the part where said light cannot permeate, for example, the back surface of the parts, namelyopposite side to the light irradiation side, especially, to the innersurface of a cylindrical parts (with hollow part). Thereby the inventorsof the present invention also proposed the fixing method of metal fineparticles comprising, irradiating a radiation which permeate a partsbeing opaque against the light belonging to the region from UV region tonear-infra red, for example, electromagnetic wave of 0.001 nm-10 nmwavelength, to the metal fine particles in the dispersion of said metalfine particles so as to fix the metal fine particles on the opaquesurface of the parts of the side where at least said radiation permeates(Japanese Patent Laid-Open Publication 2002-144378 filed on May 20,2002).

Furthermore, the inventors of the present invention investigated thecomposition of dispersing agent of metal fine particles, dispersingstability of said fine particles and photo-reactivity concerningphoto-reactivity of dispersion of metal fine particles in cases when1-dodecanethiol is used alone as a surface decorative compound of saidmetal fine particles and when from 5 to 10% of said 1-dodecanethiol issubstituted by diols [SH(C₆H₁₂)SH, SH(C₁₀H₁₂₀)SH] and reported that thedispersion of metal fine particles with high photo-reactivity can beobtained when 10% is substituted by SH(C₆H₁₂) [abstract of 38th ChemicalSociety Kyushu forum; number 1.46: Fixing of surface decorative goldnano particles by pulse laser irradiation, Effect of dithiol decorative(Jul. 19, 2001) Document 1, Photochemical forum of 2001, 50th academy ofJapan Chemical Analysis Society, p. 129 presented at 20^(th)Solid-Surface chemical forum, p 133].

Still further, the inventors of the present invention indicated theapplication to a measuring technique which utilize the improvement offunctionality as a resonance Raman sensor by the metal fine particles.And since said metal bonds with end thiol group, amino group, silylgroup or cyano group of adequate chemical structure by non-covalent bondor by covalent bond, it is known that said metal has a function toself-organize the compound having said groups.

The characteristic of the self-organizable compound is that having thiolgroup, amino group, silyl group or cyano group which bonds with saidmetal at the end, and a molecule has a chemical structure in whichintermolecular force sequenced by structure close to monomolecular film,for example, lipophilic chemical structure such as long chain alkylstructure. Further, by possessing a functional group which recognizeother adequate chemical structure besides chemical structure, forexample, a group of antigen-antibody relationship, it can be used as asensor utilizing said relationship. And, by making said sequence to astructure which can intense energy, it is possible to form a finestructure of said metal fine particles which generate the reinforcingfunction of the signal comes from said compound.

For the accomplishment of above characteristics, it is very important toconstruct a method which can achieve fixing of fine structure of saidmetal fine particles on adequate substrate surface so as to utilizeeffectively said function.

In the method proposed by the inventors of the present invention whichaggregate and fix metal fine particle from colloidal solution of metalfine particles on the surface of substrate, irradiation of electron waveof respectively high energy is necessary, and such irradiation of suchhigh energy, there is a problem to hurt the substrate to injure a photomask in a case when the irradiation is carried out through the photomask. Therefore, the establishment of a technique for fixing method ofmetal fine particles on surface of a substrate which the use of broadindustrial fields, in which said problems are dissolved.

The subject of the present invention is to provide a method to fix metalparticles on novel surface of substrate from which an inconvenience suchas injury of the substrate of the photo mask is removed, in particular,to provide a method to fix metal particles on by fine structure onsurface of a substrate by comparatively simple method which uses a photomask.

During the investigation to accomplish the method to dissolve saidsubject, the inventors of the present invention paid attention to thefact that the photo reactivity is improved by replacing 10% ofn-decylthiol which is a dispersion stabilizer used at the preparation ofcolloidal dispersion of metal fine particles, which were reported by theinventors of the present invention, with a compound e.g.1,6-hexanedithiol which can cause flocculation and fixing of metal fineparticles by relatively small energy, and investigated whether it ispossible to construct colloidal dispersion of metal fine particles whichcan cause flocculation and fixing of metal fine particles by relativelysmall energy.

In said investigation, the inventors of the present invention have foundthat flocculation and fixing of metal fine particles can be carried outby relatively small energy by following process, that is, irradiatingrelatively high power and/or high density electromagnetic wave tocolloidal dispersion of metal fine particles prepared by dispersingmetal fine particles, which are coat treated by a dispersion stabilizer,into organic solvent to which a compound being possible to causeflocculation and fixing of metal fine particles by relatively smallenergy is added, and can accomplish the method to fix metal fineparticles on the surface of substrate whose problem is dissolved by finestructure.

DISCLOSURE OF THE INVENTION

The present invention is (1) a method to fix metal fine particles onsurface of a substrate by desired fine structure corresponding to anirradiation of lower power and/or lower density electromagnetic wavecomprising;

(a) adding metal fine particles stabilized by a dispersion stabilizer,which can be released by irradiation of high energy electromagnetic waveand/or high energy density electromagnetic wave, to a solutioncontaining a dispersing agent which can be released by irradiation oflower energy electromagnetic wave and/or lower energy densityelectromagnetic wave and/or a compound which does not have bondingability to the metal fine particles to prepare a colloidal dispersion ofmetal fine particles which are a part of the dispersion stabilizer beingsubstituted with the dispersing agent and/or the compound, (b)irradiating high energy electromagnetic wave and/or high energy densityelectromagnetic wave to said prepared colloidal dispersion to release apart of the dispersion stabilizer locating on the surface of metal fineparticles and generate a dispersion of metal fine particles which isactivated so as to cause flocculation of 2-100 times larger to theoriginal particle size and to improve photo sensitivity of the metalfine particles stabilized by said dispersion stabilizer, and (c)irradiating lower energy electromagnetic wave and/or lower energydensity electromagnetic wave to said metal fine particles dispersionwhose photo sensitivity is improved by activation.

Desirably, the present invention (2) is the method to fix metal fineparticles on surface of the substrate (1) by desired fine structure,wherein the dispersion stabilizer is a compound possessing thiol group,amino group, silyl group or cyano group as a substitution group havingaffinity with metal fine particles, for example, a compound bonded withalkyl group of normal chain of carbon number 10 or more, more desirably,the present invention (3) is the method to fix metal fine particles onsurface of the substrate of (2) by desired fine structure, wherein thedispersion stabilizer is an agent used at the preparation of metalcolloidal solution by chemical reduction of a metal compound.

Further desirably, the present invention (4) is the method to fix metalfine particles on surface of a substrate of (1), (2) or (3) by desiredfine structure, wherein the compound which does not have bonding abilityto a dispersing agent released from the surface of the metal fineparticles by irradiation of electromagnetic wave of lower energy than adispersion stabilizer of metal fine particles and/or metal fineparticles is a compound whose solvent affinity part is small and/or acompound which causes the release by absorbing said electromagneticwave.

Furthermore desirably, the present invention (5) is the method to fixmetal fine particles on surface of a substrate of (1), (2), (3) or (4),wherein the particle size of the metal fine particles is from 1 nm to100 nm, still further desirably, the present invention (6) is the methodto fix metal fine particles on surface of a substrate of (5), whereinthe particle size of the metal fine particles is from 2 nm to 30 nm.

Yet further desirably, the present invention (7) is the method to fixmetal fine particles on surface of a substrate of (1), (2), (3), (4),(5) or (6), wherein the dispersing solvent is at least one selected fromthe group consisting of alicyclic hydrocarbon and aromatic hydrocarbon.

BRIEF ILLUSTRATION OF THE DRAWINGS

FIG. 1 is a drawing to illustrate a theory of fixing of metal nanoparticles by 2 steps irradiation of the present invention. (c) metalnano particles fixing pattern (MI) is formed. (a) is the activationprocess (AS) of particles in solvent by irradiation of high intensitypulse light (said second harmonic generation (SHG) laser (532 nm), 10Hz, 33 mj/pulse) from high intensity light source HLS, and (b) is thefixing process (FS) by irradiating patterned light (said 7 mJ/pulse )through a mask MS using low intensity light source LLS, then (c) metalnano particles fixing pattern (MI) which is micro alloyed is formed.

FIG. 2 shows the difference of fixing amount between DTAu (Δ, colloidalsolution 1) and HDAu (◯, colloidal solution 2). It become clear that bysame irradiation energy, DTAu (◯) can fix larger amount gold. This isobviously understood from the relationship between low intensity laserirradiation time (minutes) of dithiol substituted gold nano particles ofcolloidal solution 2 and fixing amount of gold nano particles.

FIG. 3 shoes the microscopic picture observing a pattern of fixed goldnano particles by SEM image (33 mJ/pulse) of fixed gold nano particles.

FIG. 4 indicates the characteristic of gold nano particles pattern whichis fixed by 2 steps irradiation (33 mJ/pulse, 7 mJ/pulse) of the presentinvention.

DESCRIPTION OF THE PREFERRED EMBODYMENT

The present invention will be illustrated more in detail.

A. Preparation of Metal Fine Particles;

Solution of metal fine particles used in the process to fix metal fineparticles of the present invention is the solution of metal fineparticles of particle size from 1 nm to 100 nm, desirably from 2 nm to30 nm, and is the colloidal solution which disperses particles whosesurface is protected by a dispersion stabilizer such as dodecanethiol soas to slightly released by irradiation of electromagnetic wave.Photo-reactivity of particles having large particle size is improvedrelating with particle size, however, since said particles have atendency to flocculate easily and lower dispersion stability, saidparticles are not suited for long term preservation. On the contrary,particles having relatively small particle size smaller than 2 nm issuperior at dispersion stability, however, have a tendency not to absorbeasily light of relatively lower energy and not to be photo-reactivatedeasily.

The basic concept of the present invention is, to maintain dispersionstability till the actual use, and make it possible to provideeffectively activation by irradiation of light, by replacing a part ofsaid dispersion stabilizer with a compound which does not havedispersing ability releasing from the surface of said metal fineparticles by irradiation of small and low energy electromagnetic waveand/or bonding ability to metal fine particles. Said improvement ofactivation is to prepare and use colloidal solution of metal fineparticles which can form dispersion of metal fine particles having 2nm-30 nm particle size which is 2-100 times larger particle size thanthat of stabilized dispersed metal fine particles.

As a metal to compose of said colloidal solution of metal fineparticles, a metal having plasmon absorbing band e.g. Ag, Au, Pt or Cu.In the case of gold fine particles, particles having 10 nm or less canbe prepared easily according to the method of Leff (J. Phys. Chem., 99,7036 (1995)). In this method, since dodecanethiol which disperse andstabilize formed metal fine particles is added to the prepared series,the metal fine particles are protected by the dispersion stabilizer andcan be dispersed in organic solvent such as toluene or cyclohexane,especially, can be dispersed stably in a low polar solvent.

In the case of gold fine particles prepared by above mentioned method,the gold fine particles are dispersed into dispersion in whichdodecanethiol, which is a dispersion stabilizer, and a compound whichdoes not have dispersing ability releasing from the surface of saidmetal fine particles by irradiation of small and low energyelectromagnetic wave and/or bonding ability so as to make possible tosubstitute a part of dodecanethiol, which is adsorbed to the surface offine particles after prepared with said compound. In a case when thecompound to be substituted is 1.6-hexanedithiol or cyclohexanethiol, thesubstitution of only 5% of dodecanethiol, the dispersing stability isnot spoiled. As the other compounds of said compound, it is effective tosubstitute with a compound which absorb light such as various pigmentswhich improve the photo-reactivity of metal nano particles, especially,with a pigment which releases easily from the surface of particles bythe photo reactivity of pigment itself. However, even if a compoundwhich does not absorb the irradiated light (electromagnetic wave) e.g.above mentioned dithiol compound or cyclohexanethiol, make dispersionstability in solution of metal fine particles remarkably deteriorate,for example, the fixing effect by lower energy electromagnetic and/orlower energy density electromagnetic wave can be remarkably improved bysubstitution of approximately 10%.

B. Activation;

A part of dispersion stabilizer of metal fine particles surface isreleased by irradiating electromagnetic wave of relatively strong energyto the dispersion of said metal fine particles and improve theflocculation ability of metal fine particles in dispersion. For example,in the case to irradiate second harmonic generation (SHG) laser ofNd—YAG laser, it is desirable to carry out the irradiation of 10 secondsto 3 minutes by irradiation intensity of 20 mJ/pulse-60 mJ/pulse. Excessintensity and excess time of irradiation causeflocculation•sedimentation of solution, while, activation can not becarried out by too low intensity of irradiation. Further, the light(electromagnetic) irradiation for activation is desirable to be carriedout from different direction to the irradiating direction for fixing. Byactivating particles location closely to a substrate,flocculation•sedimentation of particles in solution can be prevented andthe fixing effect to the substrate can be remarkably improved.

C. Controlling of Particle Size;

Particles to which high intense electromagnetic wave is irradiatedflocculate by releasing of a protecting agent, and are fused by absorbedenergy of electromagnetic wave so that the particle size grows up. It ispossible to control the particle size of particles to be fixed bychanging wavelength or energy of the electromagnetic wave to beirradiated, and by changing kinds of compound to be substituted with adispersing stabilizer locating on the surface of fine particles andreplacing ratio.

D. Fixation;

Metal fine particles which are activated by irradiation of saidrelatively high intense light can be easily flocculated and fixed byirradiation of relatively low intense electromagnetic wave. For example,in the case of SHG laser of Nd—YAG laser (532 nm), it is possible to fixparticles on surface of a substrate by irradiation of 6 mJ/pulse orless, however, in the case that an activation process by relatively highintense light is not carried out, fixation does not progressed at all.As the light for fixation, not only relatively low intense pulse lightsource but also CW laser or U.V. light ca be used.

E. Patterning;

The particles are fixed can be patterned by irradiating the light forfixing through chrome vapor deposition mask. Since by using coherent CWlaser a refraction pattern generator can be used for patterning ofparticles fixation, more convenient patterning of particles fixation ispossible. It is possible to use high intense pulse laser which is usedfor activation of particles for patterning of fixation as it is,however, since it damages to the mask, an expensive device which scanshigh intense laser beam spatially is needed.

F. Flocculation State Control;

When high intense pulse laser is irradiated to the particles solution,particles are fused by absorbed photon energy and fixed by formingspherical isolated particles. When low intense electromagnetic wave isused for particle fixation, it is hard to cause the fusing of particles.Therefore, it is possible to fix particle flocculated body on asubstrate by maintaining the flocculation structure in the solution. Bycontrolling the flocculation structure of particles, it becomes possibleto design the characteristics as a particle group. For example, aparticles flocculation structure which is suited for a sensor forsurface enhanced Raman or surface enhanced infrared absorption can berealized.

EXAMPLE

The present invention will be illustrated specifically, however, notintending to limit the scope of the present invention.

Reference Example 1

Acceleration of Fixing of Gold Nano Particles

Process 1; For the preparation of gold fine particles, the method ofLeff et al document was used. Chloride aureate was transferred toorganic phase (toluene) by tetraoctylammoniumbromide, and surfacedecorated gold nano particles (DTAu, 22±0.5 nm) with DT by reducing withhydrogenated sodium boride were prepared. Obtained particles weredispersed into cyclohexane (0.43 mg/mL) (colloidal solution 1) and usedfor an experiment of laser irradiation.

Process 2; DTAu particles prepared by said process 1 was dispersed intocyclohexane solution containing 0.9 mM of DT and 0.1 mM of hexanediol,and gold nano particles (HDAu, 27±0.5 nm) wherein a part of DT locatingon the surface of said DTAu particles is substituted by HD was prepared.HDAu in thiol solution was washed, then dispersed in cyclohexane (0.32mg/mL) and was used for an experiment of laser irradiation (colloidalsolution 2).

Absorption spectrum of two kinds of colloidal solution (1 and 2) weremeasured and by adding cydohexane slowly and prepared to adjust theabsorbance of absorption peak at 532 nm becomes 0.5.

Preparation of a Substrate for Metal Fine Particles Fixation.

A cover glass (Matsunami, 18×18 mm, 0.12-0.17 mm) was soaked intoboiling mix solution of aqueous ammonia (28%)/aqueous hydrogen peroxide(30%) (1:1) for several minutes so as the surface to hydrophilizate.

Fixation of Metal Fine Particles;

Said substrate is soaked into DTAu (colloidal solution 1) or HDAu(colloidal solution 2) contained in a glass cell (20×10×5 mm) and SHGlaser (532 nm, 10 Hz, 33 mJ/pulse)of Nd—YAG laser (product of ContinumCo., Ltd., Surelite I) was irradiated [FIG. 1; (a) shows the activationprocess (AS) of particles in solution by high intense pulse light (HLS)irradiation from high intense light source HLS (in this case, same laserwas used and intensity was changed), (b) shows the fixation process (FS)by low intense pulse light which is patterned through mask (MS) from lowintense light source LLS, and (c) shows micro alloyed metal nanoparticles fixed pattern (MI)]. Ultraviolet and visible ray absorptionspectrum of gold fixed on a substrate was measured by a multi channelspectrometer (Ocean Optics, S1024DW). Then the cover glass was soakedinto aqua regia so as to dissolve the gold fixed on the surface, andquantitated the fixed gold using ICP. MS (Yokokawa Analytical SystemsPMS2000). Further, the surface of the substrate on which gold fineparticles are fixed is observed by SEM (Hitachi S-5000). Difference ofthe amount of fixation between DTAu (colloidal solution 1) and HDAu(colloidal solution 2) are shown in FIG. 2. By the observation of FIG.2, it becomes clear that HDAu can fix more quantity of gold than DTAu,by same irradiation energy. SEM observation of the fixed DAu particlesis shown in FIG. 3. In comparison with DTAu, it is obvious thatparticles of larger particle size are fixed, and it is understood thatthe diol substitution effects to the size of fixed particles (Presentedat 2001 Photo Chemical Forum, 50^(th) Convention of Japan AnalyticalChemistry Society, 20^(th) Solid•Surface Photochemical Forum). In thiscase, the damage of a mask is not recognized by observation by nakedeyes or by a microscope.

Example 1

In this Example, above mentioned colloidal solution 2 was used, andphoto fixing property of gold fine particles fixation when theactivation process is used is used.

Irradiation by 33 mJ/pulse was carried out on cyclohexane solution ofHDAu (colloidal solution 2) (absorbancy 0.5) for 5 minutes and activatedthe solution [process (a) of FIG. 1]. A chrome vapor deposition testpattern was used as a mask (MS), irradiated by 7 mJ/pulse for 5 minutesand a fixation pattern of gold nano particles was prepared [process (b)of FIG. 1]. Since the chrome vapor deposition mask (MS) is damagedviolently, it can not be used directly for the preparation of a fixationpattern. The pattern of gold nano particles fixed by irradiation ofabove mentioned 7 mJ/pulse is shown in FIG. 4 [corresponding to process(c) of FIG. 1]. It was possible to fix gold particles by patterning onthe surface of substrate without damaging the mask. It was understoodthat resolvability of several ten micro meter can be easily obtained bya method to provide a chrome vapor deposition mask to the outer surfaceof the cell.

As mentioned above, it is obvious that the fine structure composed ofmetal fine particles flocculation can be formed without deterioratingthe material of substrate by electromagnetic wave in short time byflocculating and fixing the metal fine particles from the dispersion ofmetal fine particles by at least two processes of electromagnetic waveirradiation.

POSSIBILITY FOR THE INDUSTRIAL APPLICABILITY

In the present invention, a part of dispersion stabilizer of metal fineparticles substituted by a compound which does not have similardispersing ability to the dispersion agent released from the surface ofsaid metal fine particles by irradiation of lower energy electromagneticwave than said dispersion agent and previously photo activate metal fineparticles in solution, and the irradiation energy and irradiation timenecessary in a continuation fixing process can be remarkably reduced.Consequently, the technique of pattern fixation of metal fine particles(group) is improved remarkably from the conventional technique, and itbecome possible to be used as the production technique for a micro alloysensor.

1. A method to fix metal fine particles on surface of a substrate bydesired fine structure corresponding to irradiation of lower powerand/or lower density electromagnetic wave comprising; (a) adding fineparticles stabilized by a dispersion stabilizer which can be released byirradiation of high energy electromagnetic wave and/or high energydensity electromagnetic wave to a solution containing a dispersing agentwhich can be released by irradiation of lower energy electromagneticwave and/or lower energy density electromagnetic wave and/or a compoundwhich does not have bonding ability to the metal fine particles toprepare a colloidal dispersion of metal particles which are part of thedispersion stabilizer being substituted with the dispersing agent and/orcompound, (b) irradiating said high energy electromagnetic wave and/orhigh energy density electromagnetic wave to said prepared colloidaldispersion to release a part of the dispersion stabilizer locating onthe surface of metal fine particles and generate a dispersion of metalfine particles which is activated so as to cause flocculation of 2-100times larger to the original particle size and to improve photosensitivity of the metal fine particles stabilized by said dispersionstabilizer, and (c) irradiating lower energy electromagnetic wave and/orlower energy density electromagnetic wave to said metal fine particlesdispersion whose photo sensitivity is improved by activation.
 2. Themethod to fix metal fine particles on surface of the substrate bydesired fine structure of claim 1, wherein the compound which does nothave bonding ability to a dispersing agent released from the surface ofthe metal fine particles by irradiation of electromagnetic wave of lowerenergy than a dispersion stabilizer of metal fine particles and/or metalfine particles is a compound whose solvent affinity part is small and/ora compound which causes the release by absorbing said electromagneticwave.
 3. The method to fix metal fine particles on surface of thesubstrate by desired fine structure of claim 1, wherein the dispersionstabilizer is a compound possessing thiol group, amino group, silylgroup or cyano group which has high affinity with metal fine particles.4. The method to fix metal fine particles on surface of the substrate bydesired fine structure of claim 1, wherein the dispersion stabilizer isa compound possessing thiol group, amino group, silyl group or cyanogroup which has high affinity with metal fine particles, and thecompound which does not have bonding ability to a dispersing agentreleased from the surface of the metal fine particles by irradiation ofelectromagnetic wave of lower energy than a dispersion stabilizer ofmetal fine particles and/or metal fine particles is a compound whosesolvent affinity part is small and/or a compound which causes therelease by absorbing said electromagnetic wave.
 5. The method to fixmetal fine particles on surface of the substrate by desired finestructure of claim 3, combining same kinds of electromagnetic waveshaving different energy intensity and/or different energy density andcarrying out at least two steps of irradiation process ofelectromagnetic wave comprising, at least one step of irradiationprocess by high energy intensity electromagnetic wave and/or high energydensity electromagnetic wave and at least one step of irradiationprocess by low energy intensity electromagnetic wave and/or low energydensity electromagnetic wave.
 6. The method to fix metal fine particleson surface of the substrate by desired fine structure of claim 4,combining same kinds of electromagnetic waves having different energyintensity and/or different energy density and carrying out at least twosteps of irradiation process of electromagnetic wave comprising, atleast one step of irradiation process by high energy intensityelectromagnetic wave and/or high energy density electromagnetic wave andat least one step of irradiation process by low energy intensityelectromagnetic wave and/or low energy density electromagnetic wave. 7.The method to fix metal fine particles on surface of the substrate bydesired fine structure of claim 6, wherein the particle size of themetal fine particles stabilized by a dispersion stabilizer is from 1 nmto 100 nm.
 8. The method to fix metal fine particles on surface of thesubstrate by desired fine structure of claim 1, wherein the particlesize of the metal fine particles stabilized by a dispersion stabilizeris from 1 nm to 100 nm.
 9. The method to fix metal fine particles onsurface of the substrate by desired fine structure of claim 3, whereinthe particle size of the metal fine particles stabilized by a dispersionstabilizer is from 1 nm to 100 nm.
 10. The method to fix metal fineparticles on surface of the substrate by desired fine structure of claim4, wherein the particle size of the metal fine particles stabilized by adispersion stabilizer is from 1 nm to 100 nm.
 11. The method to fixmetal fine particles on surface of the substrate by desired finestructure of claim 1, wherein the dispersing solvent is at least oneselected from the group consisting of alicyclic hydrocarbon and aromatichydrocarbon.
 12. The method to fix metal fine particles on surface ofthe substrate by desired fine structure of claim 3, wherein thedispersing solvent is at least one selected from the group consisting ofalicyclic hydrocarbon and aromatic hydrocarbon.
 13. The method to fixmetal fine particles on surface of the substrate by desired finestructure of claim 4, wherein the dispersing solvent is at least oneselected from the group consisting of alicyclic hydrocarbon and aromatichydrocarbon.
 14. The method to fix metal fine particles on surface ofthe substrate by desired fine structure of claim 5, wherein thedispersing solvent is at least one selected from the group consisting ofalicyclic hydrocarbon and aromatic hydrocarbon.
 15. The method to fixmetal fine particles on surface of the substrate by desired finestructure of claim 6, wherein the dispersing solvent is at least oneselected from the group consisting of alicyclic hydrocarbon and aromatichydrocarbon.
 16. The method to fix metal fine particles on surface ofthe substrate by desired fine structure of claim 7, wherein thedispersing solvent is at least one selected from the group consisting ofalicyclic hydrocarbon and aromatic hydrocarbon.